Ab initio studies of the dipole polarizabilities of conjugated molecules. Part 6. The geometry, static dipole polarizability and first hyperpolarizability of benzothiophene

Hinchliffe, Alan; Machado, Humberto J. Soscún

doi:10.1016/0166-1280(94)03952-h

Cited by 12 publications

(15 citation statements)

References 17 publications

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“…In previous work, we have shown that reliable ab initio values of α can be obtained for neutral conjugated polyaromatic hydrocarbons by using the analytic CPHF method and the standard STO/6-31+G(md, np) selection of basis sets [12,13]. For example, for neutral naphthalene, this procedure with the STO/6-31+G basis set leads to values of α components at the Hartree-Fock level that are in excellent agreement with experimental data [12].…”

Section: Theory and Methodssupporting

confidence: 57%

“…In addition, for the naphthalene charged species the polarizability was evaluated with different basis sets, and the STO/6-31+G(d, p) basis set was the most extended one. These basis sets include sufficient diffuse sp-type and polarization functions for the accurate ab initio determination of dipole polarizabilities [12,13].…”

Section: Theory and Methodsmentioning

confidence: 99%

“…In order to help solve this problem at ab initio level it is necessary to find reliable and feasible methods to determine the polarizability of neutral and charged molecules. We have found that good values for the static dipole polarizabilities of neutral benzene and naphthalene molecules can be obtained using the analytic Coupled Perturbed Hartree-Fock (CPHF) method, at Hartree-Fock and correlated levels, and a selection of STO/6-31+G(md, np) basis sets [12,13]. In this paper we apply our methodology to present the first systematic ab initio SCF-MO study of the static dipole polarizability of the charged species of naphthalene, using optimized geometries of neutral, mono-and dication, and mono-and dianion of naphthalene.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the static dipole polarizability of neutral and charged naphthalene

Machado

Hinchliffe

1997

Elect J Theoret Chem

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SUMMARYWe present an ab initio SCF-MO study of the static dipole polarizability of some neutral and charged species of naphthalene (C10H8) q , (q = −2, −1, 0, +1, +2). The charged species involve additions and removals of electrons to and from the HOMO and LUMO π-electron orbitals. The polarizability calculations were performed using the Coupled Perturbed Hartree-Fock method, and in addition, we used direct analytical differentiation of the energy expression. We used a series of split valence basis sets augmented with sp diffuse and polarized functions STO/6-31+G(md,np, (m = n = 1, 2, 3), and all geometries were fully optimized. Molecular structure optimizations were generally started from the geometry predicted for neutral naphthalene with D2h symmetry at the HF/6-31G** level of theory.The Hartree-Fock results indicate that the anisotropies of the components of the dipole polarizability tensor of neutral naphthalene (q = 0) are in agreement with our own previous theoretical calculations and with the experimental values corresponding to laser Stark spectroscopy in a naphthalene molecular beam. This agreement with experimental results can be further improved with extension of the number of polarized functions in the basis set.We also analyse the effect of the negative and positive charges on the naphthalene molecule on the polarizability tensor components. The variation of molecular geometry also plays a part in these changes.

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Section: Theory and Methodssupporting

confidence: 57%

Section: Theory and Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the static dipole polarizability of neutral and charged naphthalene

Machado

Hinchliffe

1997

Elect J Theoret Chem

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“…In all cases, a full molecular geometry optimization was achieved, where all molecular variables were named differently and allowed to vary independently. In Tables 1, 2 and 3, the main geometrical parameters of these optimized structures are compared with those of previous quantum-mechanical works [10,11] and with experimental data [29].…”

Section: Molecular Structure Of Organicsmentioning

confidence: 99%

“…In this context, theoretical calculations can be a useful tool in understanding the experimental behavior. Quantum-mechanic calculations have been applied to the study of these molecules [10,11]. Also atomistic calculations have been applied to the study of adsorption of organics on silicate surfaces, [12][13][14][15][16] and other minerals [17].…”

Section: Introductionmentioning

confidence: 99%

Molecular structure and spectroscopic properties of polyaromatic heterocycles by first principle calculations: spectroscopic shifts with the adsorption of thiophene on phyllosilicate surface

2009

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The molecular and electronic structure and spectroscopic properties of thiophene, benzothiophene, and dibenzothiophene molecules have been studied theoretically, using different levels of quantum-mechanical calculations based on Hartree-Fock and density functional theory (DFT) approximations. In all calculation levels used, the molecular structures, dipole moments, thermodynamic properties, and vibration normal modes agree well with the available experimental data and predict the nonavailable values. The calculated frequencies agree with experimental values within scale factors in the range of 0.94-1.0 for thiophene. Our calculations have refined the mode assignments previously reported. The adsorption of thiophene on a pyrophyllite surface along the 001 plane was also investigated by means of a quantum-mechanical method based on the DFT approximation in a periodical crystal lattice model. The adsorbed thiophene adopts a parallel orientation with respect to the phyllosilicate surface. The shifts observed experimentally in the IR bands of thiophene upon adsorption on pyrophyllite are well reproduced in the thiophene-phyllosilicate complex, finding explanations of this phenomenon and new effects with our calculations.

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Hydrogenation Reactions

2002

Organometallic Modeling of the Hydrodesulfurization and Hydrodenitrogenation Reactions

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Ab initio studies of the dipole polarizabilities of conjugated molecules. Part 6. The geometry, static dipole polarizability and first hyperpolarizability of benzothiophene

Cited by 12 publications

References 17 publications

Ab initio study of the static dipole polarizability of neutral and charged naphthalene

Ab initio study of the static dipole polarizability of neutral and charged naphthalene

Molecular structure and spectroscopic properties of polyaromatic heterocycles by first principle calculations: spectroscopic shifts with the adsorption of thiophene on phyllosilicate surface

Hydrogenation Reactions

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